Photoelectric conversion device and method of making the same

ABSTRACT

A photoelectric conversion device has a non-single-crystal semiconductor laminate member formed on a substrate having a conductive surface, and a conductive layer formed on the non-single-crystal semiconductor laminate member. The non-single-crystal semiconductor laminate member has such a structure that a first non-single-crystal semiconductor layer having a P or N first conductivity type, an I-type second non-single-crystal semiconductor layer and a third non-single-crystal semiconductor layer having a second conductivity type opposite the first conductivity type are laminated in this order. The first (or third) non-single-crystal semiconductor layer is disposed on the side on which light is incident, and is P-type. The I-type non-single-crystal semiconductor layer has introduced thereinto a P-type impurity, such as boron which is distributed so that its concentration decreases towards the third (or first) non-single-crystal semiconductor layer in the thickwise direction of the I-type layer.

This application is a continuation of Ser. No. 06/785,586, filed Oct. 8,1985, which itself was a division of application Ser. No. 06/564,213filed Dec. 22, 1983, both now abandoned.

CROSS REFERENCE TO RELATED APPLICATION

This application is a continuation of Ser. No. 08/408,781, filed Mar.22, 1995, now abandoned; which is a reissue application for U.S. Pat.No. 5,077,223, which issued from Ser. No. 07/443,015, filed Nov. 29,1989; which is a continuation of Ser. No. 06/785,586, filed Oct. 8,1985, now abandoned; which is a divisional of Ser. No. 06/564,213 filedDec. 22, 1983, now U.S. Pat. No. 4,581,476; which is acontinuation-in-part of Ser. No. 06/525,459, filed Aug. 22, 1983, nowU.S. Pat. No. 4,591,892.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to a photoelectric conversion device whichhas a non-single-crystal semiconductor laminate member having formedtherein at least one PIN junction, and a method for the manufacture ofsuch a photoelectric conversion device.

2. Description of the Prior Art

A photoelectric conversion device of the type including anon-single-crystal semiconductor laminate member having formed thereinat least one PIN junction usually has the non-single-crystalsemiconductor laminate member formed on a substrate having a conductivesurface and a conductive layer formed on the non-single-crystalsemiconductor laminate member. The non-single-crystal semiconductorlaminate member has at least a first non-single-crystal semiconductorlayer of a P or N first conductivity type, an I type secondnon-single-crystal semiconductor layer formed on the firstnon-single-crystal semiconductor layer and a third non-single-crystalsemiconductor layer formed on the second non-single-crystalsemiconductor layer and having a second conductivity type opposite fromthe first conductivity type. The first, second and thirdnon-single-crystal semiconductor layers form one PIN junction.

In this case, for example, the substrate has such a structure that alight-transparent conductive layer is formed as a first conductive layeron a light-transparent insulating substrate body. The first and thirdnon-single-crystal semiconductor layers of the non-single-crystalsemiconductor laminate member are P- and N-type, respectively. Further,the conductive layer on the non-single-crystal semiconductor laminatemember is formed as a second conductive layer on the N-type thirdnon-single-crystal semiconductor layer.

With the photoelectric conversion device of such a structure asdescribed above, when light is incident on the side of thelight-transparent substrate towards the non-single-crystal semiconductorlaminate member, electron-hole pairs are created by the light in theI-type second non-single-crystal semiconductor layer. Holes of theelectron-hole pairs thus created pass through the P-type firstnon-single-crystal semiconductor layer to reach the first conductivelayer, and electrons flow through the N-type third non-single-crystalsemiconductor layer into the second conductive layer. Therefore,photocurrent is supplied to a load which is connected between the firstand second conductive layers, thus providing a photoelectric conversionfunction.

In conventional photoelectric conversion devices of the type describedabove, however, since the I-type second non-single-crystal semiconductorlayer is formed to contain oxygen with a concentration above 10²⁰atoms/cm³, and/or carbon with a concentration above 10²⁰ atoms/cm³,and/or phosphorus with a concentration as high as above 5×10¹⁷atoms/cm³, the I-type non-single-crystal semiconductor layer inevitablycontains impurities imparting N conductivity type, with far lowerconcentrations than in the P-type first non-single-crystal semiconductorlayer and the N-type third non-single-crystal semiconductor layer.

In addition, the impurity concentration has such a distribution that itundergoes substantially no variations in the thickness direction of thelayer.

On account of this, in the case where the second non-single-crystalsemiconductor layer is formed thick with a view to creating therein alarge quantity of electron-hole pairs in response to the incidence oflight, a depletion layer, which spreads into the secondnon-single-crystal semiconductor layer from the PI junction definedbetween the P-type first and the I-type second non-single-crystalsemiconductor layers, and a depletion layer, which spreads into thesecond non-single-crystal semiconductor layer from the NI junctiondefined between the N-type third and the I-type secondnon-single-crystal semiconductor layers, are not linked together. Inconsequence, the second non-single-crystal semiconductor layer has, overa relatively wide range thickwise thereof at the central region in thatdirection, a region in which the bottom of the conduction band and thetop of the valence band of its energy band are not inclined in thedirections, necessary for the holes and electrons to drift towards thefirst and third non-single-crystal semiconductor layers, respectively.Therefore, the holes and electrons of the electron-hole pairs created bythe incident light in the second non-single-crystal semiconductor layer,in particular, the electrons and holes generated in, the central regionof the second layer in its thickness direction, are not effectivelydirected to the first and third non-single-crystal semiconductor layers,respectively.

Accordingly, the prior art photoelectric conversion devices of theabove-described structure have the defect that even if the secondnon-single-crystal semiconductor layer is formed thick for creating alarge quantity of electron-hole pairs in response to incident light, ahigh photoelectric conversion efficiency cannot be obtained.

Further, even if the I-type second non-single-crystal semiconductorlayer is thick enough to permit the depletion layer extending into thesecond non-single-crystal semiconductor layer from the PI junctionbetween the P-type first non-single-crystal semiconductor layer on theside on which light is incident and the I-type second non-single-crystalsemiconductor layer formed on the first semiconductor layer and thedepletion layer extending into the second non-single-crystalsemiconductor layer from the NI junction between the N-type thirdnon-single-crystal semiconductor layer on the side opposite from theside of the incidence of light and the I-type second non-single-crystalsemiconductor layer to be linked together, the expansion of the formerdepletion layer diminishes with the lapse of time for light irradiationby virtue of a known light irradiation effect commonly referred to asthe Staebler-Wronsky effect, because the I-type non-single-crystalsemiconductor layer forming the PI junction contains impurities whichimpart N conductivity type as mentioned previously. Finally, theabovesaid depletion layers are disconnected from each other. Inconsequence, there is formed in the central region of the secondnon-single-crystal semiconductor layer in the thickness directionthereof a region in which the bottom of the conduction band and the topof the valence band of the energy band are not inclined in thedirections in which the holes and electrons of the electron-hole pairscreated by the incidence of light are drifted towards the first andthird non-single-crystal semiconductor layers, respectively.

Accordingly, the conventional photoelectric conversion devices of theabovesaid construction have the defect that the photoelectric conversionefficiency is impaired by the long-term use of the devices.

SUMMARY OF THE INVENTION

It is therefore an object of the present invention to provide a novelphotoelectric conversion device which is able to achieve a far higherphotoelectric conversion efficiency than that obtainable with theconventional devices described above.

Another object of the present invention is to provide a novelphotoelectric conversion device the photoelectric conversion efficiencyof which is hardly or only slightly lowered by the Staebler-Wronskieffect even if it is used for a long period of time.

Yet another object of the present invention is to provide a novel methodwhich permits easy manufature of the photoelectric conversion devicehaving the abovesaid excellent features.

In accordance with an aspect of the present invention, the first (orthird) non-single-crystal semiconductor layer of the non-single-crystallaminate member is a layer on the side on which light is incident and isof P conductivity type, and the I-type second non-single-crystalsemiconductor layer has introduced therein an impurity for impartingthereto P type conductivity, which is distributed so that the impurityconcentration continuously decreases towards the third (or first)non-single-crystal semiconductor layer in the thickness direction of theI-type layer.

In this case, for example, the substrate is light-transparent and,accordingly, the first non-single-crystal semiconductor layer isdisposed on the side where light is incident. The first and thirdnon-single-crystal semiconductor layers are P- and N-type, respectively,and the I-type second non-single-crystal semiconductor layer hasintroduced therein an impurity for imparting thereto P-typeconductivity, such as boron, so that its concentration in the regionadjacent the first non-single-crystal semiconductor layuer is higherthan the concentration in the region adjacent the thirdnon-single-crystal semiconductor layer.

On account of this, even if the I-type second non-single-crystalsemiconductor layer is formed relatively thick for creating therein alarge quantity of electron-hole pairs in response to the incidence oflight, the depletion layer extending into the second non-single-crystalsemiconductor layer from the PI junction between the first and secondnon-single-crystal semiconductor layers and the depletion layerextending into the second non-single-crystal layer from the NI junctionbetween the third and second non-single-crystal semiconductor layers arejoined together. Accordingly, the holes and electrons which are producedin the central region of the second non-single crystal semicondutorlayer in its thickwise direction are also effectively drifted towardsthe first and third non-sinlge-crystal semiconductor layers,respectively.

Moreover, even if the I-type second non-single-crystal semiconductorlayer contains impurities which impart thereto N-type conductivity,because it is formed to contain oxygen and/or carbon and phosphorus inlarge quantities as described previously, boron, which imparts P-typeconductivity and is introduced into the second non-single-crystalsemiconductor layer, combines with oxygen, and/or carbon, and/orphosphorus. Besides, the P-type impurity introduced into the secondnon-single-crystal semiconductor layer has a high concentration in theregion thereof adjacent the P-type first non-single-crystalsemiconductor layer, that is, on the side of the PI junction. Therefore,the expansion of the depletion layer spreading into the secondnon-single-crystal semiconductor layer from the PI junction between thefirst and second non-single-crystal semiconductor layers is scarcely oronly slightly diminished by the light irradiation effect (theStaeabler-Wronski effect).

Accordingly, the photoelectric conversion device of the presentinvention retains a high photoelectric conversion efficiency, even ifused for a long period of time.

In accordance with another aspect of the present invention, the secondnon-single-crystal semiconductor layer, which has introduced thereintoan impurity which imparts P-type conductivity, with such a distributionthat its concentration continuously decreases towards the N-type third(or first) non-single-crystal semiconductor layer in the thicknessdirection of the second layer, can easily be formed, through a CVD(Chemical Vapor Deposition) method using a semiconductor material gasand an impurity material gas for imparting P-type conductivity, merelyby continuously decreasing (or increasing) the concentration of thedepart material gas relative to the semiconductor material gas with thelapse of time.

Accordingly, the manufacturing method of the present invention allowsease in the fabrication of the photoelectric conversion device of thepresent invention which possesses the aforementioned advantages.

Other objects, features and advantages of the present invention willbecome more fully apparent from the detailed description take inconjunction with the accompanying drawings.

BRIEF DESCRIPTION OF THE DRAWINGS

FIGS. 1A to D are sectional views schematically illustrating a sequenceof steps involved in the manufacture of a photoelectric conversiondevice in accordance with an embodiment of the present invention;

FIG. 2A is a sectional view schematically illustrating a firstembodiment of the photoelectric conversion device by the manufacturingmethod shown in FIG. 1;

FIG. 2B is a graph showing the concentration distributions of impuritiesintroduced into first, second, and third non-single-crystalsemiconductor layers of the photoelectric conversion device depicted inFIG. 2A;

FIG. 2C is a graph showing the energy band of the photoelectricconversion device shown in FIG. 2A;

FIG. 3 is a graph showing the voltage V (volt)current density I (mA/cm²)characteristic of the photoelectric conversion device of FIG. 2, incomparison with the characteristric of a conventional photoelectricconversion device;

FIG. 4 is a graph showing variations (%) in the photoelectric conversionefficiency of the photoelectric conversion device of the presentinvention, shown in FIG. 2, in comparison with a conventionalphotoelectric conversion device;

FIG. 5A is a sectional view schematically illustrating a secondembodiment of the photoelectic conversion device of the presentinvention;

FIG. 5B is a graph showing concentration distributions of impuritiesintroduced into first second, and third non-single-crystal semiconductorlayers of the second embodiment of the present invention;

FIG. 6A is a sectional view sechematically illustrating a thirdembodiment of the photoelectric conversion device of the presentinvention; and

FIG. 6B is a graph showing the concentration distributions of impuritiesintroduced into first, second, and third non-single-crystalsemiconductor layers of the photoelectric conversion device shown inFIG. 6A.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

A description will be given of, with reference to FIGS. 1 and 2, of afirst embodiment of the photoelectric conversion device of the presentinvention, along with the manufacturing method of the present invention.

The manufacture of the photoelectric conversion device starts with thepreparation of an insulating, light transparent substrate 1 as of glass(FIG. 1).

A light-transparent conductive layer 2 is formed on the substrate 1(FIG. 1B).

The conductive layer 2 is formed of, for example, a tin oxide, or alight-transparent conductive material consisting principally of a tinoxide. The conductive layer 2 is formed by, for example, a known vacuumevaporation method to a thickness of, for instance, 0.1 to 0.2 μm.

Next, a non-single-crystal semiconductor laminate member 3 is formed onthe conductive layer 2 (FIG. 1C).

The non-single-crystal semiconductor laminate member 3 has such astucture that a P-type non-single-crystal semiconductor layer 4, anI-type non-single-crystal semiconductor layer 5 and an N-typenon-single-crystal semiconductor layer 6 are sequentially formed in thisorder. These non-single-crystal semiconductor layers 4, 5 and 6 form aPIN junction.

The non-single-crystal semiconductor layer 4 of the non-single-crystalsemiconductor laminate member 3 is formed of, for example, Si,Si_(x)C_(1-x) (where 0<×<1, for instance, ×=0.8) or Ge in an amorphous,semiamorphous, or microcrystalline form. The non-single-crystalsemiconductor layer 4 is, for example, 100 angstroms thick. Moreover,the energy band gap of layer 4 is preferably larger than that of layer5.

The non-single-crystal semiconductor layer 4 is formed by a CVD methodwhich employs a semiconductor material gas composed of a hydride orhalide of a semiconductor, such as Si, Si,Ge_(1-x) (where oxl), or Ge,and an impurity material gas composed of a hydride or halide of a P-typeimpurity, for instance, diborane (B₂H₆), The CVD method may or may notemploy a glow discharge (plasma), or light. In this casenon-single-crystal semiconductor layer 4 has a p-type impurityintroduced therein (boron) in a concentration above about 1×10¹⁸ and ashigh as 1×10¹⁹ to 6×10²⁰ atoms/cm³, as shown in FIG. 2B.

The non-single-crystal semiconductor Iayer 5 is formed of, for instance,amorphous or semi-amorphous silicon, and has a thickness of, forexample, 3 to 0.8 μm, in particular, 0.5 μm.

The non-single-crystal semiconductor layer 5 is formed by a CVD methodwhich uses a semiconductor raw material gas composed of a hydride orhalide of silicon, for example, Si_(n)H_(2n+2) (where n is greater thanor equal to 1), or SiF_(m) (where m is greater than or equal to 2), anda deposit material gas composed of a hydride or halide of a P-typeimpurity, for instance, diborane (B₂H₆), the CVD method may or may notemploy a glow discharge (plasma), or light. In this case, by decreasingthe concentration of the deposit material gas relative to theconcentation of the semiconductor material gas within a range of lessthan 5 ppm with the lapse of time, the non-single-crystal semiconductorlayer 5 is formed having introduced thereinto a P-type impurity (boron)the concentration of which linearly and continuously decreases in thethickness direction of the layer towards the non-single-crystalsemiconductor layer 6 as shown in FIG. 2B. The concentration of theP-type impurity in the non-single-crystal semiconductor layer 5 is highon the side of the non-single-crystal semiconductor layer 4 as comparedwith the impurity concentration on the side of the non-single-crystalsemiconductor layer 6. The ratio of the impurity concentration in thelayer 5 at one end thereof adjacent the layer 6 to the concentration atthe other end adjacent the layer 4 is 1/10 to 1/100, preferably, 1/20 to1/40. In practice, the P-type impurity (boron) has a concentration of2×10¹⁵ to 2×10¹⁷ atoms/cm³ at the end of the layer 5 adjacent the layer4 and a concentration below 1×10¹⁵ atoms/cm³ at the end of the layer 5adjacent the layer 6.

The non-single-crystal semiconductor layer 5 is formed by the abovesaidabove said CVD method. In this case, the semiconductor raw material gasis one that is obtained by passing a semiconductor raw material gasthrough a molecular sieve or zeolite which adsorbs oxygen, and/or carbonand/or phosphorus. Accordingly, the non-single-crystal semiconductorlayer 5 is formed to contain oxygen at a concentration less than 5×10¹⁹atoms/cm³ as low as 5×10¹⁸ atoms/cm³, and/or carbon at a concentrationlevel less than 4×10¹⁹ 4×10 ¹⁸ atoms/cm³ as low as 4×10¹⁵ atoms/cm³,and/or phosphorus at a concentration at least as low as 5×10¹⁵atoms/cm³.

The non-single-crystal semiconductor layer 6 is formed of, for instance,microcrystalline silicon, and has a thickness of, for example, 100 to300 angstroms. Moreover, the energy band gap of layer 6 is preferablylarger than that of layer 5.

The non-single-crystal semiconductor layer 6 is formed by a CVD methodwhich employs a semiconductor raw material gas composed of a hydride orhalide of silicon, for example, Si_(n)H_(2n+2) (where n is greater thanor equal to 1) or SiF_(m) (where m is greater than or equal to 2), andan impurity material gas composed of a hydride or halide of an N-typeimpurity, for instance, phosphine (PH₃), the CVD method may or may notemploy a glow discharge (plasma) or light. In this case, thenon-single-crystal semiconductor layer 6 has an N-type impurity(phosphorus) introduced thereinto with a concentration of 1×10¹⁹ to6×10²⁰ atoms/cm³, as shown in FIG. 2.

Next, a conductive layer 7 is formed on the non-single-crystalsemiconductor laminate member 3 made up of the non-single-crystalsemiconductor layers 4, 5. Moreover, the energy band gap of layer 6 is,preferably larger than that of layer 5. and 6, that is, on thenon-single-crystal semiconductor layer 6 (FIG. 1D).

The conductive layer 7 has such a structure that a light-transparentconductive layer 8 formed of, for example, a tin oxide or alight-transparent conductive material consisting principally of tinoxide, and a reflective conductive layer 9 formed of a metal, such asaluminum, silver or the like, are formed in this order. In this case,the conductive layer 8 is formed to a thickness of 900 to 1300 angstromsby means of, for example, vacuum evaporation, and the conductive layer 9is also formed by vacuum evaporation.

In the manner described above, the first embodiment of the photoelectricconversion device of the present invention shown in FIG. 2A ismanufactured.

With the photoelectric conversion device shown in FIG. 2A, when light 10is incident on the side of the substate 1 towards the non-single-crystalsemiconductor laminate member 3, electron-hole pairs are created in theI-type non-single-crystal semiconductor layer 5 in response to the light10. The holes of the electron-hole pairs thus produced flow through theP-type non-single-crystal semiconductor layer 4 into thelight-transparent conductive layer 2, and the electrons flow through theN-type non-single-crystal semiconductor layer 6 into the conductivelayer 7. Therefore, photocurrent is supplied to a load which isconnected between the conductive layers 2 and 7, thus providing thephotoelectric conversion function.

In this case, the I-type non-single-crystal semiconductor layer 5 has aP-type impurity (boron) introduced thereinto which is distributed sothat the impurity concentration continuously decreases towards thenon-single-crystal semiconductor layer 6 in the thickness direction ofthe layer 5, as shown in FIG. 2B. On account of this, even if the I-typenon-single-crystal semiconductor layer 5 is formed thick for generatingtherein a large quantity of electraonhole pairs in response to theincident of light, a depletion layer (not shown) which extends into thenon-single-crystal semiconductor layer 5 from the PI junction 11 betweenthe P-type non-single-crystal semiconductor layer 4 and the I-typenon-single-crystal semiconductor layer 5 and a depletion (not shown)layer which extends into the non-single-crystal semiconductor layer 5from the NI junction 12 between the N-type non-single-crystalsemiconductor layer 6 and the non-single-crystal semiconductor layer 5are joined together. Therefore, the I-type non-single-crystalsemiconductor layer 5, as viewed from the bottom of the conduction bandand the top of the valence bands of its enegy band, has a gradient thateffectively causes holes and electrons drift towards thenon-single-crystal semiconductor layers 4 and 6, respectively.

Accordingly, the photoelectric conversion device of the presentinvention, shown in FIG. 2A, achieves a higher photoelectric conversionefficiency than do the conventional photoelectric conversion devices.

A photoelectric conversion device corresponding to the conventional oneand which is identical in construction with the photoelectric conversiondevice of the present invention shown in FIG. 2A, except that theconcentration of the N-type impurity in the I-type non-single-crystalsemiconductor layer 5 is about 10¹⁶ atoms/cm³ which is far lower thanthe impurity concentrations in the P-type and I-type non-single-crystalsemiconductor layers 4 and 6 because the I-type non-single-crystalsemiconductor layer 5 is formed to contain oxygen, and/or carbon, and/orphosphorus in large quantities, as referred to previously, provided avoltage V (volt)-current density I (mA/cm²) characteristic as indicatedby curve 30 in FIG. 3. Accordingly, the open-circuit voltage was 0.89 V,the short-circuit current density I 16.0 mA/cm², the fill factor was61%, and the photoelectric conversion efficiency about 8.7%. In contrastthereto, the photoelectric conversion device of the present inventionshown in FIG. 2A, provided the voltage V -current density Icharacteristic as indicated by curve 31 in FIG. 3, obtained.Accordingly, the open-circuit voltage V was 0.92 V, which is higher thanwas with the abovesaid device corresponding to the prior art device; thecurrent density I was 19.5 mA/cm²; the fill factor was 68%; and thephotoelectric conversion efficiency was about 12.2%. Incidentally, theseresults were obtained under the conditions wherein the photoelectricconversion devices, each having the non-single-crystal semiconductorlaminate member 3 of a 1.05 cm² area, were exposed to irradiation bylight with an intensity of AM1 (100 mW/cm²).

In the case of the photoelectric conversion device of a presentinvention shown in FIG. 2A, since the I-type non-single-crystalsemiconductor layer 5 has boron introduced thereinto as a P-typeimpurity the boron, combines with the oxygen and/or carbon and/orphosphorus contained in the non-single-crystal semiconductor layer 5. Inaddition, the concentration of the P-type impurity (boron) is high onthe side of the PI junction 11, that is, on the side of the P-typenon-single-crystal semiconductor layer 4. Accordingly, the expansion ofthe depletion layer extending into the I-type non-single-crystalsemiconductor layer 5 from the PI junction 11 between the P-typenon-single-crystal semiconductor layer 4 and the I-typenon-single-crystal semiconductor layer 5 is hardly or only slightlydiminished by the light irradiation effect (the Staebler-Wronskieffect).

For this reason, according to the photoelectric conversion device of thepresent invention, the aforesaid high photoelectric conversionefficiency is hardly impaired by long-term use.

In addition the aforesaid photoelectric conversion device correspondingto the prior art one which provided the voltage V-current density Icharacteristeristic indicated by the curve 30 in FIG. 3, exhibitedvariations (%) in the photoelectric conversion efficiency relative tothe light irradiation time T (hr) as indicated by curve 40 in FIG. 4. Incontrast thereto, in the case of the photoelectric conversion device ofthe present invention, the photoelectric conversion efficiency variedwith the light irradiation time T as indicated by curve 41 in FIG. 4.That is, the photoelectric conversion efficiency slightly increased inan early stage and, thereafter, it decreased only very slightly withtime. These result were also obtained under the same conditionsmentioned previously in connection with FIG. 3.

As described above, the first embodiment of the photoelectric conversiondevice of the present invention possesses the advantage that it providesa higher photoelectric conversion efficiency than do the conventionalphotoelectric conversion devices, even when used for a long period oftime.

Further, the manufacturing method of the present invention shown in FIG.1 employs a series of simple steps such as forming the conductive layer2 on the substrate 1, forming the non-single-crystal semiconductorlayers 4, 5 and 6 on the conductive layer 2 through the CVD method toprovide the non-single-crystal semiconductor laminate member 3 andforming the conductor layer 7 on the non-single-crystal semiconductorlaminate member 3, The I-type non-single-crystal semiconductor layer 5is formed by a CVD method using a semiconductor raw material gas and aP-type deposit (boron) gas and, in this case, simply by continuouslychanging the concentration of the deposit material gas relative to theconcentration of the semiconductor raw material gas as a function oftime, the P-type impurity is introduced into the layer 5 with such aconcentration distribution that its concentration continuously decreasestowards the non-single-crystal semiconductor layer 6 in the thicknessdirection of the layer 5.

Accordingly, the manufacturing method of the present invention allowsease in the fabrication of the photoelectric conversion device of thepresent invention which has the aforementioned advantages.

Incidentally, the first embodiment illustrated in FIG. 2 shows the casein which the impurity contained in the I-type non-single-crystalsemiconductor layer 5 has such a concentration distribution as shown inFIG. 2B in which the concentration linearly and continuously dropstowards the non-single-crystal semiconductor layer 6.

As will be appreciated from the above, however, even if the impurityintroduced in the I-type non-single-crystal semiconductor layer 5 has aconcentration profile such that the impurity concentration dropsstepwise and continuously towards the non-single-crystal semiconductorlayer 6 as shown in FIG. 5 which illustrates a second embodiment of thepresent invention, and even if the impurity in the layer 5 has such aconcentration distribution that the impurity concentration decreasesnon-linearily and continuously towards the layer 6 in a manner to obtaina concentration distribution such that the impurity concentrationabruptly drops in the end portion of the layer 5 adjacent the layer 6 asshown in FIG. 6 which illustates a third embodiment of the presentinvention, the photoelectric conversion device of the present inventionproduces the same excellent operation and effects as are obtainable withthe photoelectric conversion device shown in FIG. 2.

Further, the foregoing description has been given of the case wherelight is incident on the photoelectric conversion device from the sideof the substrate 1 and, accordingly, the non-single-crytal semiconductorlayer 4 of the non-single-crystal semiconductor laminate member 3 on theside on which the light is incident is P-type.

But, also in case where the photoelectric conversion device is arrangedto be exposed to light on the side opposite from the substrate 1, thenon-single-crystal semiconductor layer 6 of the non-single-crystalsemiconductor laminate member 3 on the side of the incidence of light isP-type, the non-single-crystal semiconductor layer 4 on the side of thesubstrate 1 is N-type and the non-single-crystal semiconductor layer 5has introduced thereinto a P-type impurity (boron) which is distributedso that the impurity concentration continuously decreases towards thenon-single-crystal semiconductor layer 4 in the thickness direction ofthe layer 5, the same excellent operation and effects as describedpreviously can be obtained, as will be understood from the foregoingdescription. In this case, however, the conductive layer 7 must besubstituted with a light-transparent one. The substrate 1 and theconductive layer 2 need not be light-transparent.

While in the foregoing the non-single-crystal semiconductor laminatemember 3 has one PIN junction, it is also possible to make the laminatemember 3 have two or more PIN junctions and to form each of the two ormore I-type non-single-crystal semiconductor layers so that the P-typeimpurity introduced therein may have the aforesaid concentrationdistribution.

It will be apparent that many modifications and variations may beeffected without departing from the scope of the novel concepts of thepresent invention.

1. A method for manufacturing a photoelectric conversion device comprising the steps of: forming a first impurity, non-single crystalline semiconductor layer of a first conductivity type on a substrate in a reaction chamber; depositing a substantially intrinsic semiconductor layer on said first impurity layer by introducing process gas into said reaction chamber together with a dopant gas comprising boron, the introducing ratio of said dopant gas to said process gas being monotonically decreased throughout the deposition of the intrinsic semiconductor layer in order that the impurity concentration in said intrinsic semiconductor layer is monotonically decreased from the interface between said first impurity and intrinsic semiconductor layers; forming a second impurity, non-single crystalline semiconductor layer of a second conductivity type opposite to said first conductivity type, the impurity semiconductor layer adjacent to the heavier doping side of said intrinsic layer having the same conductivity type as that corresponding to the dopant gas for said intrinsic semiconductor layer; forming an electrode arrangement for said conversion device; and reducing the oxygen concentration in said substantially intrinsic layer to a level less than 5×10¹⁹ atoms/cm³.
 2. A manufacturing method according to claim 1 5, wherein the process gas is a hydride or halide of silicon and the dopant gas is a hydride or halide of boron.
 3. A manufacturing method according to claim 2 5, wherein the concentration of the dopant gas relative to the concentration of the process gas is continuously decreased with time within a range of less than 5 ppm.
 4. A method as in claim 3 where 5, wherein said level is as low as 5×10¹⁸ atoms/cm³.
 5. A manufacturing method as in claim 1 where for manufacturing a photoelectric conversion device comprising the steps of: forming a first impurity, non-single crystalline semiconductor layer of a first conductivity type on a substrate in a reaction chamber; depositing a substantially intrinsic semiconductor layer on said first impurity layer by introducing process gas into said reaction chamber together with a dopant gas comprising boron, the introducing ratio of said dopant gas to said process gas being monotonically decreased throughout the deposition of the intrinsic semiconductor layer in order that the impurity concentration in said intrinsic semiconductor layer is monotonically decreased from the interface between said first impurity and intrinsic semiconductor layers; forming a second impurity, non-single crystalline semiconductor layer of a second conductivity type opposite to said first conductivity type, the impurity semiconductor layer adjacent to the heavier doping side of said intrinsic layer having the same conductivity type as that corresponding to the dopant gas for said intrinsic semiconductor layer; forming an electrode arrangement for said conversion device; and reducing the oxygen concentration in said substantially intrinsic layer to a level less than 5×10 ¹⁹ atoms/cm ³, wherein the reduction of the oxygen concentration is effected by passing said process gas through a molecular sieve or zeolite which adsorbs oxygen.
 6. A method of claim 1 5, wherein said semiconductor layer is made of amorphous semiconductor.
 7. A method of claim 6 5, wherein said process gas is filtered in advance of introduction into said reaction chamber.
 8. A method for manufacturing a photoelectric conversion device comprising the steps of: forming a first impurity, non-single crystalline semiconductor layer of a first conductivity type on a substrate in a reaction chamber; depositing a substantially intrinsic semiconductor layer on said first impurity layer by introducing process gas into said reaction chamber together with a dopant gas comprising boron, the introducing ratio of said dopant gas to said process gas being monotonically decreased throughout the deposition of the intrinsic semiconductor layer in order that the impurity concentration in said intrinsic semiconductor layer is monotonically decreased from the interface between said first impurity and intrinsic semiconductor layers; forming a second impurity, non-single crystalline semiconductor layer of a second conductivity type opposite to said first conductivity type, the impurity semiconductor layer adjacent to the heavier doping side of said intrinsic layer having the same conductivity type as that corresponding to the dopant gas for said intrinsic semiconductor layer; forming an electrode arrangement for said conversion device; and reducing the carbon concentration in said substantially intrinsic layer to a level less than 4×10¹⁹ atoms/cm³.
 9. A method as in claim 8 where 10, wherein said level is as low as 4×10¹⁵ atoms/cm³.
 10. A manufacturing method as in claim 8 method for manufacturing a photoelectric conversion device comprising the steps of: forming a first impurity, non-single crystalline semiconductor layer of a first conductivity type on a substrate in a reaction chamber; depositing a substantially intrinsic semiconductor layer on said first impurity layer by introducing process gas into said reaction chamber together with a dopant gas comprising boron, the introducing ratio of said dopant gas to said process gas being monotonically decreased throughout the deposition of the intrinsic semiconductor layer in order that the impurity concentration in said intrinsic semiconductor layer is monotonically decreased from the interface between said first impurity and intrinsic semiconductor layers; forming a second impurity, non-single crystalline semiconductor layer of a second conductivity type opposite to said first conductivity type, the impurity semiconductor layer adjacent to the heavier doping side of said intrinsic layer having the same conductivity type as that corresponding to the dopant gas for said intrinsic semiconductor layer; forming an electrode arrangement for said conversion device; and reducing the carbon concentration in said substantially intrinsic layer to a level less than 4×10 ¹⁸ atoms/cm ³ ; wherein the reduction of the carbon concentration is effected by passing said process gas through a molecular sieve or zeolite which adsorbs carbon.
 11. A method for manufacturing a photoelectric conversion device comprising the steps of: forming a first impurity, non-single crystalline semiconductor layer of a first conductivity type on a substrate in a reaction chamber; depositing a substantially intrinsic semiconductor layer on said first impurity layer by introducing process gas into said reaction chamber together with a dopant gas comprising boron, the introducing ratio of said dopant gas to said process gas being monotonically decreased throughout the deposition of the intrinsic semiconductor layer in order that the impurity concentration in said intrinsic semiconductor layer is monotonically decreased from the interface between said first impurity and intrinsic semiconductor layers; forming a second impurity, non-single crystalline semiconductor layer of a second conductivity type opposite to said first conductivity type, the impurity semiconductor layer adjacent to the heavier doping side of said intrinsic layer having the same conductivity type as that corresponding to the dopant gas for said intrinsic semiconductor layer; forming an electrode arrangement for said conversion device; and reducing the phosphorus concentration in said substantially intrinsic layer to a level less than 5×10¹⁵ atoms/cm³.
 12. A method as in claim 11 where said level is as low as 5×10¹⁵ atoms/cm³.
 13. A manufacturing method as in claim 11 where the reduction of the phosphorus concentration is effected by passing said process gas through a molecular sieve or zeolite which adsorbs phosphorus.
 14. A method as in claims 1, 8, or 11 where 5 or 10, wherein said first conductivity type is n-type and said second conductivity type is p-type.
 15. A method as in claims 1, 8, or 11 where 5 or 10, wherein said first conductivity type is p-type and said second conductivity type is n-type.
 16. A method as in claims 1, 8, or 11 where 5 or 10, wherein the ratio of said impurity concentration at the interface between said second impurity and intrinsic semiconductor layers to that at said interface between said first impurity and the intrinsic semiconductor layers is 1/10 to 1/100.
 17. A method as in claim 16 where wherein said ratio is 1/20 to 1/40.
 18. A method as in claims 1, 8, or 11 where 5 or 10, wherein said impurity is boron and the boron concentration at said interface between the p-type and intrinsic layers is 2×10¹⁵ to 2×10¹⁷ atoms/cm³.
 19. A method as in claims 1, 8, or 11 where 5 or 10, wherein said first layer comprises p-type, non-single crystalline Si_(x)C_(1-x) (0<x<1) and said impurity comprises boron. 